CO adsorbents with hysteresis

ABSTRACT

The Present Invention is directed to a composition, its synthesis and a process for adsorptive separation of carbon monoxide from gas mixtures using adsorbents, which comprise cuprous compounds on amorphous oxide macroporous supports. The compositions are prepared by impregnating cupric compounds on supports followed by reduction of the cupric compound to the corresponding cuprous compound. The reduction can be performed by the use of a reducing gas, preferably synthesis gas at relatively low temperatures up to 150° C., preferably preceded by the use of elevated temperature above 250° C. All the adsorbents described in this invention consist of CuCl particles of finite size supported on macroporous support materials including alumina and silica gel. Among the ingredients used to form supported CuCl fine particles are support materials of low dispersing power, high copper loading, absence of dispersants, and proper post heat-treatment. The bulk nature of the active component (i.e., CuCl particles) and the resulting hysteresis in desorption provide adsorbents which have both high working capacity and high selectivity for a pressure swing adsorptive separation process.

This is a division of application Ser. No. 08/235,593 filed Apr. 29,1994.

FIELD OF THE INVENTION

The Present Invention is directed to adsorptive separation of carbonmonoxide from gas mixtures using adsorbents of active compositecopper-containing compositions produced by impregnation of a supportwith cupric compounds.

BRIEF DESCRIPTION OF THE PRIOR ART

Both carbon monoxide and hydrogen are gases widely used in the chemicalindustry. The current technique used to produce both pure hydrogen andcarbon monoxide is to steam reform methane, remove carbon dioxide byscrubbing with amine solutions and finally cryogenic separation ofcarbon monoxide and hydrogen. However, there is considerable interest indeveloping an adsorption process that is capable of separating carbonmonoxide and hydrogen. The key advantages of an adsorption system overcryogenic separations are low energy requirements, capability ofproducing higher purity hydrogen and absence of any needs for liquidcryogens. The principle technical hurdle in developing an adsorptionsystem to produce high purity carbon monoxide is achieving an adsorbentthat is capable of separating dilute, unreacted methane in the steammethane reformation off-gas from bulk carbon monoxide. The carbonmonoxide over methane selectivity of an adsorbent must be high toproduce a high purity carbon monoxide stream. Chemical users of carbonmonoxide are requiring higher and higher product purity to eliminateunwanted side reaction during carbon monoxide use and the synthesis ofengineering plastics and polyurethane foams. Current methane purityspecification in carbon monoxide for many applications is nearing 25 PPMor less. Thus, an adsorbent capable of producing carbon monoxide of thispurity must demonstrate high carbon monoxide selectivity. In addition tohigh carbon monoxide selectivity, an adsorbent for this process mustalso exhibit a large carbon monoxide working capacity. The larger thecarbon monoxide working capacity, the smaller the adsorption beds andlower capital costs for such an adsorptive separation.

U.S. Pat. No. 3,789,106 discloses the use of zeolites and mordenitesthat have their sodium ions ion-exchanged with copper as well as othermetals to adsorb carbon monoxide. The main objective is to remove traceamounts of carbon monoxide from gas mixtures. In the case of thispatent, the copper ion becomes a cation replacing sodium in the zeoliticor mordenitic molecular sieve structure.

U.S. Pat. No. 4,019,879 discloses the adsorptive separation of carbonmonoxide using zeolitic molecular sieves which are ion exchanged tointroduce cations of cuprous valences into the structure. Cupric ionsmay first be impregnated in the zeolitic structure followed by reductionof the cupric ions to cuprous ions in the ion exchange procedure.

U.S. Pat. No. 4,470,829 discloses an adsorbent for selective adsorptionof carbon monoxide comprising a copper halide, an aluminum halide and apolystyrene or its derivative as one embodiment or a copper halide andaluminum halide and activated carbon or graphite as a second embodiment.The adsorbent is produced by mixing together the three components in ahydrocarbon solvent and then driving off the solvent.

U.S. Pat. No. 4,587,114 discloses the production of a carbon monoxideadsorbent using cuprous or cupric compounds impregnated on a carbonsupport using solvents which are removed after the impregnation. Thesolvents include water, aqueous hydrochloric acid or ammonium formate,primary or secondary alcohol having 1 to 7 carbon atoms, acetone,ethylacetate, formic acid, acetic acid, benzene, toluene, propionitrile,acetonitrile and aqueous ammonia.

U.S. Pat. No. 4,713,090 discloses a carbon monoxide adsorbent comprisinga composite support of silica and/or alumina and activated carbonizedmaterial carrying a copper compound impregnated with the assistance of asolvent including aqueous solutions of ammoniacal formic acid, ammoniawater and nitrogen-containing solvents selected from the group ofpropionitrile, acetonitrile, diethyl amine, dimethyl formamide andN-methyl pyrrolidone.

U.S. Pat. No. 4,914,076 discloses an adsorbent for selective adsorptionof carbon monoxide comprising a support of alumina or silica-aluminaimpregnated with a cupric salt carried by a solvent incorporating areducing agent, after which the solvent is removed and the cupric saltis reduced to a cuprous salt. The solvent utilized to deposit the cupriccompound was water containing a reducing agent. Other solventsidentified include formalin, formic acid, alcohol and the like. Thereducing agent includes low valence metal salts of iron, tin, titaniumand chromium and organic compounds in low degree of oxidation includingaldehydes, saccharides, formic acid, oxallic acid and so on.

U.S. Pat. No. 4,917,711 discloses a carbon monoxide selective adsorbentproduced from mixing in solid form or through solvent intermixing asupport from the group of zeolites, alumina, silica gel, aluminosilicate, alumino phosphate and combinations with a cuprous compound,wherein the cuprous compound can be derived from a cupric compounddeposited on the support from a solvent selected from the group ofwater, hydrochloric acid-containing aqueous solution, primary orsecondary alcohols having 1 to 7 carbon atoms, acetone, ethylacetate,hydrocarbons having 4 to 7 carbon atoms, propionitrile and acetonitrile.

U.S. Pat. Nos. 5,175,137; 5,126,310 and 5,258,571 disclose copper basedcarbon monoxide adsorbents produced by highly dispersing copper as amonolayer with a dispersant, such as ammonium citrate.

These prior art patents attempt to produce a carbon monoxide selectiveadsorbent with high dispersions of cuprous ions on a support toeffectively adsorb bulk quantities of carbon monoxide from gas mixtures.However, these adsorbents follow traditional Langmuir type isotherms inadsorption of carbon monoxide and desorption of carbon monoxide, unlikethe Present Invention. The Present Invention overcomes these limitationsby providing a novel adsorbent, having unexpectedly high hysteresis inadsorption desorption using cuprous ion on a macroporous support as willbe described in greater detail below.

BRIEF SUMMARY OF THE INVENTION

The Present Invention is an adsorbent for selectively adsorbing carbonmonoxide from a gas mixture containing carbon monoxide, comprising;cuprous chloride particles of a size in the range of approximately 1 to100 millimicrons supported on a macroporous support of an amorphousoxide.

Preferably, the cuprous chloride particles are crystalline.

Preferably, the particles are of a size in the range of approximately 16to 51 millimicrons.

Preferably, the amorphous oxide is selected from the group consisting ofalumina, silica, silica-alumina and mixtures thereof. Preferably, themacroporous support has an average pore size in the range ofapproximately 50 to 150 Angstroms.

Preferably, the macroporous support has a surface area in the range ofapproximately 100 to 600 m² /g.

Preferably, the adsorbent is prepared by contacting the support with asolution of cupric chloride to impregnate the cupric chloride on thesupport, removing the solvent, heating the impregnated support to atleast 200° C. and reducing the cupric chloride to cuprous chloride.

More preferably, the Present Invention is an adsorbent for selectivelyadsorbing carbon monoxide from a gas mixture containing carbon monoxideand at least one other gas selected from the group consisting of carbondioxide, methane and nitrogen, comprising; cuprous chloride crystallineparticles of a size in the range of approximately 1 to 100 millimicronssupported on a macroporous support of an amorphous oxide having anaverage pore size in the range of approximately 50 to 150 Angstromswherein the adsorbent is prepared by contacting the support with asolution of cupric chloride to impregnate the cupric chloride on thesupport, removing the solvent, heating the impregnated support to atleast 200° C. and reducing the cupric chloride to cuprous chloride.

The Present Invention is also a method for synthesis of an adsorbent ofcuprous chloride particles of a size in the range of approximately 1 to100 millimicrons supported on a macroporous support of an amorphousoxide for selectively adsorbing carbon monoxide from a gas mixturecontaining carbon monoxide, comprising; contacting the support with asolution of cupric chloride to impregnate the cupric chloride on thesupport, removing the solvent, heating the impregnated support to atleast 200° C. and reducing the cupric chloride to cuprous chloride.

Preferably, the solvent is removed by drying at a temperature of atleast approximately 100° C.

Preferably, heating is performed at a temperature of 250° C.

More preferably, heating is performed in an atmosphere selected from thegroup consisting of nitrogen and air.

Still more preferably, heating is performed at a temperature of 420° C.

Preferably, the cupric chloride is reduced with a reducing agentselected from the group consisting of hydrogen, carbon monoxide andsynthesis gas.

Preferably, the cupric chloride is impregnated on said support at aloading of at least 15 weight percent based upon the weight of copper tothe weight of the support.

The Present Invention is also a process of selectively separating carbonmonoxide from a gas mixture containing carbon monoxide and at least oneother gas selected from the group consisting of carbon dioxide, methaneand nitrogen, comprising; (a) contacting the gas mixture with anadsorbent comprising cuprous chloride particles of a size in the rangeof approximately 1 to 100 millimicrons supported on a macroporoussupport of an amorphous oxide, (2) selectively adsorbing carbon monoxideon the adsorbent, and (3) separately desorbing the carbon monoxide fromthe adsorbent to recover the carbon monoxide.

Preferably, the cuprous chloride particles are crystalline.

More preferably, the cuprous chloride crystalline particles undergo aphase change with the carbon monoxide to form a cuprous chloride-carbonmonoxide crystal during adsorption.

More preferably, the cuprous chloride-carbon monoxide crystals undergo aphase change during desorption of the carbon monoxide at lower pressureto form a cuprous chloride crystalline particle.

Preferably, the gas mixture is passed through one or more beds of saidadsorbent in a sequence of steps, comprising; (a) adsorbing the carbonmonoxide from the gas mixture in a bed of the adsorbent, (b) desorbingthe bed of adsorbent after adsorption, (c) purging the bed of adsorbentwith carbon monoxide, (d) evacuating the bed of adsorbent to recover thecarbon monoxide, and (e) repressurizing the bed of adsorbent to thepressure of adsorption by passing a gas into the bed of adsorbent.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 comprises x-ray diffraction patterns for a Cu/SiO₂ adsorbentbefore (a) and after (b) carbon monoxide adsorption.

FIG. 2 is a carbon monoxide isotherm for a Cu/SiO₂ adsorbent at 30° C.and 50° C. showing hysteresis.

FIG. 3 is a carbon monoxide isotherm for a Cu/Al₂ O₃ adsorbent at 30° C.showing hysteresis.

FIG. 4 is a carbon monoxide isotherm for a Cu/Al₂ O₃ adsorbent at 30° C.showing hysteresis.

FIG. 5 is a carbon dioxide isotherm for a high surface area adsorbent,LaRoche A201 Al₂ O₃, poresize 100A, surface area 325 m² /g,(microporous) and a low surface area adsorbent, Alcoa CSS-105 Al₂ O₃,surface area 113 m² /g, (macroporous) showing that the impurity carbondioxide is co-adsorbed to a greater extent on high surface areaadsorbents.

DETAILED DESCRIPTION OF THE INVENTION

The Present Invention is directed to adsorbent compositions, theirsynthesis and processes for using the adsorbent compositions toselectively adsorbed carbon monoxide from gas mixtures typically havingcarbon dioxide, hydrogen, methane, nitrogen, as well as other potentialgases or impurities. The carbon monoxide adsorbents of the PresentInvention are comprised of cuprous chloride particles supported onmacro- or mesoporous support materials, typically selected from alumina,silica, silica-alumina and silica gels. The unique feature of theadsorbent compositions is the existence of cuprous chloride particles ofa finite size serving as the active entity for carbon monoxideadsorption, wherein the cuprous chloride particle size is in the rangeof approximately 1 to 100 millimicrons, more preferably 16 to 51millimicrons. These cuprous chloride particles are preferably in ahighly crystalline state. When such a cuprous chloride crystallineparticulate adsorbent is exposed to an adequate carbon monoxidepressure, a solid cuprous chloride carbon monoxide complex is formed onthe surface of the support for the cuprous chloride. The mechanism ofcarbon monoxide uptake by the adsorbent through the formation of bulkcuprous chloride carbon monoxide complexes on the surface of theadsorbent is supported by x-ray diffraction patterns shown in FIG. 1Aand B. FIG. 1A shows that in the absence of carbon monoxide, the cuprouschloride crystalline particles supported on an appropriate amorphousoxide of the Present Invention is the dominant phase of the adsorbent,which is prepared in accordance with Example 4 below. The x-raydiffraction pattern is indicative of the crystalline nature of thecuprous chloride and the width of the peaks of the diffraction patternare indicative of particle size.

Upon carbon monoxide adsorption to saturation, the x-ray diffractionpeaks from the cuprous chloride phase become much smaller and areaccompanied by the appearance of a powder pattern corresponding tocuprous chloride carbon monoxide bulk complexes. The cuprous chloridecarbon monoxide bulk complex is identified in FIG. 1B, which shows thecharacteristic peaks for that phase change composition.

The copper loadings that are preferably achieved by the techniques ofthe Present Invention are greater than approximately 15 weight % copperbased on the total composite composition. Although on supports which donot have an inherent dispersing property, lower loadings are acceptable.

The amorphous oxide supports are compounds well known in the prior artand do not require further description. Each such support is selectedfrom those forms of amorphous oxide which have macroporous structure,particularly in contrast to the molecular size of molecules, such asmethane. More specifically, the amorphous oxide support should noteffect molecular sieving and capture of molecules, such as methane. Theamorphous oxides include alumina, silica-alumina, silica, titania andmixtures thereof. The term amorphous indicates a generallynoncrystalline molecular structure. Crystalline materials, such aszeolites are not included. The macroporosity constitutes a supportstructure that has a predominant amount of its pores larger thanapproximately 20 Angstroms in diameter up to 500 Angstroms, preferably50 to 150 Angstroms. The macroporosity is such as to avoid sieving andsurface affinity enhancements for molecules, such as methane.

The cuprous chloride active specie of the composite supported adsorbentof the Present Invention is most easily impregnated on the support inthe form of cupric chloride which is readily soluble in water as acarrier. Therefore, under most circumstances a cupric chloride reagentis mixed with water and impregnated on the amorphous oxide support withsubsequent conversion of the cupric chloride impregnate to cuprouschloride, the active carbon monoxide adsorbing specie.

Preferably, the synthesis process for producing the compositecompositions of the Present Invention includes dissolution of the cupriccompound in an aqueous solution. The addition of cupric compound on thesupport until the appropriate desired weight loading of the cupriccompound is achieved is important. For alumina supports a loading of atleast 15 wt % is desirable. Reduction of the composite composition,particularly the cupric ion to cuprous ion, by contact with a reducinggas at temperatures greater than 100° C., such as carbon monoxidehydrogen or synthesis gas (a combination of H₂, CO, as well aspotentially CO₂, methane and nitrogen) is also important. Alternatively,heating, preferably in an inert gas, in the range of approximately 150°to 450° C., preferably at least 200° C., more preferably at least 250°C., followed by contact with the reducing gas assists in providing thehighest activity of the composition.

FIG. 2 displays the carbon monoxide uptake or isotherm of a cuprouschloride-silicon dioxide adsorbent of the Present Invention as thefunction of equilibrium carbon monoxide pressure at 30° and 50° C. Twosets of data were obtained for each temperature. The lower or adsorptionbranch was obtained by starting with a clean adsorbent and usingincreasing equilibrium carbon monoxide pressure, while the upper ordesorption branch was obtained by starting with a carbon monoxidesaturated sample at high equilibrium pressure and working down to lowequilibrium pressure. The isotherms shown in FIG. 2 differ from theLangmuir-type isotherms obtained from carbon monoxide adsorbents basedupon an atomically dispersed cuprous chloride. There is a largehysteresis between adsorption and desorption; that is, there areseparate adsorption and desorption branches of the isotherm. Secondly,the shape of the isotherms does not change significantly withtemperature. Instead the isotherm shifts toward higher pressure withincreasing temperature. Thirdly, both adsorption and desorption branchesexhibit phase-transition-like behavior, that is, sudden change in carbonmonoxide uptake in a small pressure differential region. These regionsare referred to as phase transition regions. All of these three featurescan be uniquely attributed to the formation of cuprouschloride-carbon-monoxide crystallites on the adsorbent surface, whereincarbon monoxide is adsorbed in a bulk particle of 1 to 100 millimicronswithin the crystal lattice of the cuprous chloride adsorbent specie, incontrast to the adsorption of carbon monoxide by atomic size layers ofcuprous chloride in prior adsorbents.

The shape of the adsorption branches of the isotherms in FIG. 2 indicatethat there is little atomically dispersed cuprous chloride on theadsorbent surface of the Present Invention, because little carbonmonoxide uptake is observed in the low pressure region, such as below2.7 atmospheres at 30° C. If there were atomically dispersed cuprouschloride on the surface of the adsorbents of the Present Invention andif the uptake of carbon monoxide were due to chemical adsorption ofcarbon monoxide, one would observe Langmuir-type isotherms in thispressure region. Therefore, the present inventors believe that thecarbon monoxide uptake by the adsorbents of the Present Invention aredue to a mechanism other than mere chemical adsorption, that is;formation of a bulk copper-CO complex.

The shape of the desorption branch of the isotherms shown in FIG. 2 isdetermined by the thermodynamics of the decomposition of the cuprouschloride-carbon monoxide bulk complex. The kinetic barrier associatedwith the phase transition from cuprous chloride particles into cuprouschloride-carbon monoxide particles results in a threshold pressure forcarbon monoxide adsorption to occur, thereby, leading to the hysteresisillustrated in FIG. 2. The temperature dependence of the adsorbent isalso unique, shifting toward the high pressure side with increasingtemperature due to the nature of the cuprous chloride-carbon monoxideformation and decomposition.

Copper in the reduced state, either copper in the valence of one orcopper metal is active for carbon monoxide binding, the copper in abivalent state is not. However, copper in the bivalent salt state isvery soluble in aqueous solution, while copper in the monovalent saltstate is sparingly soluble in either strong acid or base. Hence,compositions where adsorbents are produced from bivalent copper,followed by in situ reduction to monovalent copper or metal are easierand less expensive to produce.

The following examples describe techniques to make carbon monoxideadsorbents of the Present Invention.

EXAMPLE 1

44.4 grams of Davison grade 59 silica gel, pre-dried in air at 600° C.for 4 hours, was impregnated with a solution of 17.0 grams of AldrichCuCl₂.2H₂ O and 48.8 mil deionized water, dried in air at 120° C. for 12hours followed by heat-treatment in nitrogen (APCI, zero grade) at 420°C. for 6 hours. The sample was activated with a syngas mixture at 150°C. for 12 hours prior to isotherm measurements. The CO isotherms fromthis sample at 30° and 50° C. are displayed in FIG. 2. It can be seenthat the isotherms consist of an adsorption and desorption branch, i.e.,a strong hysteresis in desorption. At 30° C., this adsorbent has a COsaturation capacity of 1.6 mmole/g at 7 atm, and a working capacity of1.2 mmole/g between 0.1 and 1.0 atm.

EXAMPLE 2

5.05 pounds of LaRoche A201 alumina, pre-dried in air at 400° C. for 14hours, was impregnated with a solution consisting of 970 grams ofAldrich CuCl₂.2H₂ O and 915 ml of deionized water, dried in air at roomtemperature for 5 hours and at 129° C. for 15 hours. The above samplewas again impregnated with a solution consisting of 850 g AldrichCuCl₂.2H₂ O and 802 ml of deionized water, followed by drying in air atroom temperature for 4 hours and drying in nitrogen at 250° C. for 15hours. The sample was activated in a syngas mixture at 150° C. for 15hours. The isotherm of the sample at 30° C., shown in FIG. 3, exhibitshysteresis. The CO capacity at 8.5 atm is 1.8 mmole/g and the CO workingcapacity between 0.1 and 1.0 atm is 1.1 mmole/g.

EXAMPLE 3

40 grams of Alcoa CSS-105 alumina was impregnated with a solutionconsisting of 21.1 grams of Aldrich CuCl₂.2H₂ O and 28 ml deionizedwater, dried in air at room temperature overnight, then dried innitrogen at 250° C. for 7 hours, and finally activated in a syngasmixture at 150° C. for 11 hours. The isotherm of the sample at 30° C. isshown in FIG. 4. The sample shows hysteresis and has a CO capacity of1.7 mmole/g at 8 atm and a CO working capacity of 1.4 between 0.1 and 1atm. The low surface area of the support material of the sample (113 m²/g) leads to lower CO₂ uptake as compared with the sample prepared fromhigh surface area support (325 m₂ /g), as shown in FIG. 5, indicative ofhigher selectivity in the low surface area support based adsorbent.

EXAMPLE 4

24 grams of Davison grade 59 silica gel, pre-dried in air at 600° C. for6 hours, was impregnated with a solution consisting of 13.5 grams ofAldrich CuCl₂.2H₂ O and 27 ml of deionized water, dried in air at roomtemperature for 8 hours and at 120° C. for 12 hours. The sample was thentreated in nitrogen at 420° C. for 6 hours and activated in a syngasmixture at 150° C. for 15 hours. The resulting adsorbent exhibitshysteresis and has a saturation CO capacity of 2.1 mmole/g at 6 atm anda CO working capacity of 1.9 mmole/g between 0.1 and 1 atm.

EXAMPLE 5

20 grams of Davison grade 636 silica gel, pre-dried at 600° C. for 6hours, was impregnated with a solution containing 12.8 grams of AldrichCuCl₂.2H₂ O and 16 ml of deionized water, dried in air at roomtemperature for 7 hours and at 120° C. for 12 hours. The sample was thentreated in nitrogen at 420° C. for 5 hours and activated in a syngasmixture at 150° C. for 14 hours. The resulting adsorbent exhibitshysteresis and has a CO saturation capacity at 7 atm of 1.4 mmole/g.

EXAMPLE 6

160.6 grams of Alcoa CSS-105 alumina was impregnated with a solutioncontaining 78.8 grams of Aldrich CuCl₂.2H₂ O and 75 ml of deionizedwater, dried in air at room temperature for 15 hours and at 250° C. for6 hours. Upon activation in a syngas mixture at 150° C. for 15 hours,the sample exhibits hysteresis and has a CO capacity of 1.25 mmole/g at6.6 atm.

The range of copper loading for generating CuCl particles, thereforehysteresis, depends on the dispersing power of support materials. Forthe support with poor dispersing ability toward CuCl such as silica gel,any loading will result in the formation of CuCl particles and isothermswith hysteresis. For alumina that has high dispersing ability, copperloadings above 15 wt % are preferred to generate appropriately sizedCuCl particles on the surface.

EXAMPLE 7

80 grams of LaRoache A201 alumina was impregnated with a solutionconsisting of 25.3 grams of Aldrich CuCl₂.2H₂ O and 36 ml of deionizedwater, dried in air at room temperature for 23 hours and at 120° C. for12 hours. The sample was then treated in nitrogen at 420° C. for 6 hoursand activated in syngas mixture at 150° C. for 15 hours. The resultingadsorbent has a CO capacity at 7.7 atm of 0.81 mmole/g, but littlehysteresis. The copper loading of this sample is only 11.6 wt %.

Heat treatment following impregnation and air drying at 120° C. is alsodesireable to produce isotherms with substantial hysteresis. The postheat treatment can be conducted both in nitrogen or in air attemperatures above 250° C.

EXAMPLE 8

25 grams of Davison grade 59 silica gel, pre-dried in air at 580° C. for15 hours, was impregnated with a solution containing 2.4 grams ofAldrich CuCl₂.2H₂ O and 27 ml of deionized water, dried in air at roomtemperature for 5 hours and 120° C. for 12 hours. Upon activation in asyngas mixture, the sample exhibited a CO capacity of 0.26 mmole/g at7.5 atm without hysteresis. After the sample was treated in nitrogen at420° C. for 6 hours, it showed hysteresis and a CO capacity of 0.34mmole/g at 7.5 atm.

The utility of the adsorbents produced by the Present Invention is in apressure swing adsorptive separation process to recover carbon monoxide.The steps include (1) pressurization with pure hydrogen countercurrentto the direction of feed to superambient pressure (200 psig), (2) feedwith a gas mixture containing carbon monoxide, methane, hydrogen andnitrogen at 200 psig, (3) cocurrent depressurization of the column to 25psig. (This depressurization effluent is recycled to the feed end of thebed to insure high carbon monoxide recovery), (4) cocurrent purge withproduct carbon monoxide at 0 to 5 psig and (5) evacuation of pure carbonmonoxide product at vacuum levels of 80 torr. Then the cyclic process iscontinued from steps 1 through 5.

The Present Invention differs from the traditional CuCl-based COadsorbents in the patent literature in the physical form of the activecomponent (i.e., CuCl), the mechanism of the interaction between CO andthe adsorbents, and the preparation used to achieve the desired form ofthe active component. The adsorbents of the Present Invention rely onCuCl particles of size ranging from 1 to 100 millimicrons, as opposed tothe highly dispersed CuCl of the known adsorbents. Adsorption of CO onthe adsorbents of the Present Invention is carried out by the reactionof CO with fine CuCl particles on the support surfaces, forming bulkCuCl(CO) complex. This process involves both Cu--CO bond formation andCu--Cl bond cleavage, i.e., phase transition from CuCl to CuCl(CO)crystals. This phase transition is evidenced by the x-ray diffractionpowder patterns shown in FIG. 1. The consequence of this interaction isthe hysteresis in the CO isotherms as shown in FIGS. 2 to 4. Thepreparation for the current adsorbents is aimed at forming CuClparticles on the support surface. This is achieved by: 1) using supportswith poor dispersing ability (e.g., silica gel), 2 ) using high copperloading when the support has strong dispersing power (e.g., alumina), 3)not using dispersing reagents, and 4) proper post heat-treatment (seeExample 8).

The reason that macroporous support materials are used in the pastpreparations is to improve the CO selectivity over gases such as CH₄ andCO₂. The drawback of using macroporous supports in the known adsorbentsis the resulting low capacity of the adsorbents. However, both highworking capacity and high selectivity can be attained from theadsorbents of the Present Invention. The high working capacity isachieved through: 1) the bulk nature of the active component (i.e.,surface CuCl particles, and 2) the hysteresis in desorption. The bulknature enables more CuCl to be loaded on the surface of a supportmaterial, leading to high overall CO capacity. The hysteresis holds COon the adsorbent surface in the depressurization step of pressure swingor vacuum swing adsorption operation, resulting in high workingcapacity. The high selectivity of the adsorbent is obtained by using alow surface area support without a significant loss in working capacity(Example 3). The adsorbents of the Present Invention also exhibit twoadditional features useful for an adsorptive CO separation process.First, the hysteresis enables the depressurization to proceed to a verylow pressure (e.g., 0.4 atm at 30° C.) without significant loss of COfrom the adsorbent surface. This enables a process to employ vacuumpurge, therefore, consuming less CO and achieving high CO productivity.The other feature is due to the temperature dependence of the isothermof the adsorbent of the Present Invention. For example, at 50° C., thedesorption isotherm of the adsorbent of the Present Invention will beabove 1 atm, making possible a pressure swing adsorption operation.

Recently the purity specification for carbon monoxide have become morestringent, requiring very low methane impurities of the order of 25 ppmin the carbon monoxide product. Adsorbents produced by the techniquesdescribed in the Present Invention are capable of separating methanefrom carbon monoxide to produce high purity carbon monoxide productshaving less than 25 ppm of methane. In this way, the compositecompositions of the Present Invention overcome the drawbacks and effecta solution to outstanding problems in the industry utilizing high puritycarbon monoxide.

The Present Invention has been set forth with regard to severalpreferred embodiments, but the full scope of the invention should beascertained from the claims which follow.

We claim:
 1. A process of selectively separating carbon monoxide from agas mixture containing carbon monoxide and at least one other gasselected from the group consisting of carbon dioxide, methane andnitrogen, comprising; (a) contacting said gas mixture with an adsorbentcomprising cuprous chloride particles of a size in the range ofapproximately 16 to 51 millimicrons supported on a macroporous supportof an amorphous oxide selected from the group consisting of silica,alumina, silica-alumina and mixtures thereof, said adsorbent exhibitinga substantial hysteresis between the adsorption and desorptionisotherms, (2) selectively adsorbing carbon monoxide on said adsorbentat a pressure above 0.3 atmospheres, and (3) separately desorbing saidcarbon monoxide from said adsorbent to recover said carbon monoxide. 2.The process of claim 1 wherein said cuprous chloride particles arecrystalline.
 3. The process of claim 2 wherein said cuprous chloridecrystalline particles undergo a phase change with said carbon monoxideto form a cuprous chloride-carbon monoxide crystal during adsorption. 4.The process of claim 3 wherein said cuprous chloride-carbon monoxidecrystals undergo a phase change during desorption of said carbonmonoxide.
 5. The process of claim 1 wherein said gas mixture is passedthrough one or more beds of said adsorbent in a sequence of steps,comprising; (a) adsorbing said carbon monoxide from said gas mixture ina bed of said adsorbent, (b) desorbing said bed of adsorbent afteradsorption, (c) purging said bed of adsorbent with carbon monoxide, (d)evacuating said bed of adsorbent to recover said carbon monoxide, and(e) repressurizing said bed of adsorbent to the pressure of adsorptionby passing a gas into said bed of adsorbent.